阅读说明：本技术 一种2，2-二氟丙醇的生产工艺 (Production process of 2, 2-difluoropropanol ) 是由 闫宗刚 葛繁龙 茅嘉龙 邹学明 王春雷 黄凯华 于 2020-09-16 设计创作，主要内容包括：本发明公开了一种2,2-二氟丙醇的生产工艺,步骤一、加成反应：用N_2置换高压釜内的空气,加入甲醇和交联剂,升温到130℃,在0.5MPa下,慢慢通入二氟氯乙烯,控制釜压不超过0.5MPa,反应24小时；步骤二、加氢反应：把催化剂钯碳加入到反应釜中,甲醇作为溶剂,加入三乙胺,通入氢气,增压至2MPa,在110℃下,反应24小时,反应结束后,过滤回收钯碳,然后在95℃,常压下精馏回收甲醇；在120℃,常压下精馏得到产品。本发明比传统用2,2-二氟丙酸酯还原法原料便宜,而且三废少、制备的产物收率高,纯度好,原料易得,工艺简单,稳定性好,对设备要求简单,制备的2,2-二氟丙醇更适合工业化生产。(The invention discloses a production process of 2, 2-difluoropropanol, which comprises the following steps: with N 2 Replacing air in the autoclave, adding methanol and a cross-linking agent, heating to 130 ℃, slowly introducing difluorochloroethylene under 0.5MPa, controlling the kettle pressure not to exceed 0.5MPa, and reacting for 24 hours; step two, hydrogenation reaction: adding catalyst palladium-carbon into a reaction kettle, using methanol as a solvent, adding triethylamine, introducing hydrogen, pressurizing to 2MPa, reacting for 24 hours at 110 ℃, filtering and recovering the palladium-carbon after the reaction is finished, and rectifying at 95 ℃ and normal pressure to recover the methanol; rectifying at 120 deg.C under normal pressure to obtainAnd (5) producing the product. Compared with the traditional 2, 2-difluoropropionate reduction method, the method has the advantages of cheap raw materials, less three wastes, high yield of the prepared product, good purity, easily obtained raw materials, simple process, good stability and simple requirement on equipment, and the prepared 2, 2-difluoropropanol is more suitable for industrial production.)

1. A production process of 2, 2-difluoropropanol is characterized in that: the method comprises the following steps:

step one, addition reaction: with N₂Replacing air in the autoclave, adding methanol and a cross-linking agent, heating to 130 ℃, slowly introducing difluorochloroethylene under 0.5MPa, controlling the kettle pressure not to exceed 0.5MPa, and reacting for 24 hours;

step two, hydrogenation reaction: adding catalyst palladium carbon into a reaction kettle, wherein the mass ratio of difluorochloroethylene to palladium carbon is 1: 0.5, taking methanol as a solvent, adding triethylamine, wherein the mass ratio of the triethylamine to the difluorochloroethylene is 2: 1, introducing hydrogen, pressurizing to 2MPa, reacting for 24 hours at 110 ℃, filtering and recovering palladium-carbon after the reaction is finished, and rectifying and recovering methanol at 95 ℃ and normal pressure; rectifying at 120 ℃ and normal pressure to obtain the product 2, 2-difluoropropanol.

2. The process for the production of 2, 2-difluoropropanol according to claim 1, characterized in that: in the first step, the cross-linking agent is 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.

3. The process for the production of 2, 2-difluoropropanol according to claim 1, characterized in that: in the first step, the mass ratio of difluorochloroethylene to methanol is controlled to be 1: 4-1: 6.

4. the process for the production of 2, 2-difluoropropanol according to claim 1, characterized in that: and in the second step, triethylamine is used as an acid-binding agent to absorb hydrochloric acid generated by the reaction.

Technical Field

The invention particularly relates to a production process of 2, 2-difluoropropanol.

Background

Difluorodichloroethane (R132b) is a byproduct in industrial production of R123a, and in recent years, with the application of R123a, the waste of fluorine resources caused by the treatment of R132b as hazardous waste is increasing. The invention synthesizes difluorochloroethylene prepared by R132b into 2, 2-propanol, which is an important way to change waste into valuable.

The traditional 2, 2-propanol process is to use 2, 2-difluoro methyl propionate to reduce and generate 2, 2-propanol, but the preparation of 2, 2-difluoro methyl propionate needs to use expensive dust reagent, so that the cost of 2, 2-propanol is greatly increased. Compared with the traditional reduction method using 2, 2-difluoro methyl propionate, the process has the advantages of cheap raw materials, less three wastes, high yield of prepared products, good purity, easily obtained raw materials, simple process, good stability and simple requirement on equipment, and the prepared 2, 2-difluoro propanol is more suitable for industrial production.

Disclosure of Invention

The purpose of the invention is as follows: in order to solve the defects of the prior art, the invention provides a production process of 2, 2-difluoropropanol.

The technical scheme is as follows: a production process of 2, 2-difluoropropanol comprises the following steps:

step one, addition reaction: with N₂Replacing air in the autoclave, adding methanol and a cross-linking agent, heating to 130 ℃, slowly introducing difluorochloroethylene under 0.5MPa, controlling the kettle pressure not to exceed 0.5MPa, and reacting for 24 hours;

step two, hydrogenation reaction: adding catalyst palladium carbon into a reaction kettle, wherein the mass ratio of difluorochloroethylene to palladium carbon is 1: 0.5, taking methanol as a solvent, adding triethylamine, wherein the mass ratio of the triethylamine to the difluorochloroethylene is 2: 1, introducing hydrogen, pressurizing to 2MPa, reacting for 24 hours at 110 ℃, filtering and recovering palladium-carbon after the reaction is finished, and rectifying and recovering methanol at 95 ℃ and normal pressure; rectifying at 120 ℃ and normal pressure to obtain the product 2, 2-difluoropropanol.

As an optimization: in the first step, the more crosslinking agents used in production are dicumyl peroxide, benzoyl peroxide, dicumyl hydroperoxide and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane. The invention determines that the best effect is achieved when the cross-linking agent is 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.

As an optimization: in the first step, the mass ratio of difluorochloroethylene to methanol is controlled to be 1: 1-1: 10, the reaction can be carried out, and the invention determines that the reaction is carried out at a mass ratio of 1: 4-1: the best effect is obtained after 6 times.

As an optimization: in the second step, the acid-binding agent generally comprises organic base and inorganic base, wherein the organic base comprises triethylamine, DIEA, pyridine and the like, and the inorganic base comprises sodium acetate, sodium carbonate, potassium carbonate and the like. The invention determines that triethylamine is used as an acid-binding agent, and the effect of absorbing hydrochloric acid generated by reaction is optimal.

Has the advantages that: the product prepared by the method has the advantages of high yield, good purity, easily obtained raw materials, simple process, good stability and simple requirement on equipment, and the prepared 2, 2-difluoropropanol is more suitable for industrial production.

Detailed Description

Examples

A production process of 2, 2-difluoropropanol comprises the following steps:

step one, addition reaction: with N₂Replacing air in the autoclave, adding methanol and a crosslinking agent, wherein the crosslinking agent is 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, heating to 130 ℃, slowly introducing difluorochloroethylene under 0.5MPa, and controlling the mass ratio of the difluorochloroethylene to the methanol to be 1: 4-1: 6, controlling the kettle pressure not to exceed 0.5MPa, and reacting for 24 hours;

step two, hydrogenation reaction: adding catalyst palladium carbon into a reaction kettle, wherein the mass ratio of difluorochloroethylene to palladium carbon is 1: 0.5, taking methanol as a solvent, adding triethylamine, taking triethylamine as an acid-binding agent to absorb hydrochloric acid generated by the reaction, wherein the mass ratio of the triethylamine to the difluorochloroethylene is 2: 1, introducing hydrogen, pressurizing to 2MPa, reacting for 24 hours at 110 ℃, filtering and recovering palladium-carbon after the reaction is finished, and rectifying and recovering methanol at 95 ℃ and normal pressure; rectifying at 120 ℃ and normal pressure to obtain the product 2, 2-difluoropropanol.

The product prepared by the method has the advantages of high yield, good purity, easily obtained raw materials, simple process, good stability and simple requirement on equipment, and the prepared 2, 2-difluoropropanol is more suitable for industrial production.

The technical solutions in the embodiments of the present invention are clearly and completely described above, so that those skilled in the art can better understand the advantages and features of the present invention, and thus the protection scope of the present invention is more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.